Plasticized elastomer compositions containing n-(hydroxyalkyl)-amides and their fatty acid esters



Patenterl June 28, 1949 2,474,793 PLASTICIZED ELASTOMER COMPOSI- TIONS CONTAINING N-(HYDROXY- ALKYL)-AMIDES AND THEIR FATTY ACID ESTERS Philip F. Tryon, Terre Haute,

Solvents Corporation,

Commercial Ind., assignor to Terre Hante,

Ind., a corporation of Maryland No Drawing.

Application J anuaryS, 1945,

Serial No. 571,9.65 4 Claims. (Cl. 260-32.2)

This invention relates to plasticized elastomer compositions and more particularly to such compositions m which so-called synthetic rubbers are plasticized or softened with softening agents of the class of N-(hydroxyalkyl) amides of lower fatty acids and their fatty acid esters, the N-(alkanecarbonyloxyalkyl) amides.

In the manufacture and compounding of rubber and synthetic rubber, it is necessary to bring the compound into a plastic state so that pigments, fillers, and the like can be incorporated therein, and so that the product can be molded into the desired shape before vulcanizing. In the ca-se'of natural rubber, simple heating by the friction of milling on a roller mill induces the necessary degree of plasticity for these purposes.

The so-called synthetic rubbers or synthetic elastomers on the other hand do not respond easily to milling treatment and often become hard and brittle or crumble when subjected to such milling. It is, therefore, essential to add to many of the synthetic elastomers softening or plasticizing agents to facilitate satisfactory milling and forming operations.

It is desirable that such softeners not only plasticize the elastomer, but that they shall not seriously decrease the tensile strength and stretching capacities of the plasticized material.

I have found that N-(hydroxyalkyl) and N- alkanecarbonyloxyalkyl) amides of lower fatty acids are excellent plasticizers for synthetic elastomers and impart their beneficial softening properties without damage to the tensile strength and elongation characteristics of the resulting composition, in many cases actually enhancing one or the other or both of these characteristics to some extent.

The amides utilizable as softening agents in my invention may be represented by the following structural formula in which R an alkyl radical having from 1 to carbon atom-s, 1'1. represents a substituent selected from the group consisting of hydroxymethyl and --CH2--O--CO--CH3, R is a substituent selected from a group consisting of hydrogen and methyl and R is a substituent selected from the group consisting of ethyl and ---CH2-O--CO-CH2.

The softening agents of my invention may be employed in conjunction with any of the synthetic rubbers prepared by polymerization of 1,3-butadiene alone or copolyinerized with other polymerizable monomers, which contain the polymerizable structure H2C=C among which may be mentioned the arylolefins such as styrene and vinyl naphthalene; the alpha-methylene carboxylic acids and their esters, nitriles and amides such as acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile methacrylonitrile, methacrylamide, isobutylene, methyl vinyl ether and so on. My softening agents are especially effective when utilized with butadieneacrylonitrile copolymers, which are generally recognized as among the most difficult of the elastomers to plasticize.

within the scope of my invention may be mentioned the following; 2-formamido-1-butanol; 2-acetainido-1- butanol; 2-butanamido-1-butanol; 2 hexan amido-l-butanol; 2-acetamido-2-rnethyl-1-pronol; 2-acetamido-2-methyl-1,3-propanediol; acetotris hydroxymethyl methylamide; 2-acetamidobutyl acetate; 2-acetamido-2-rnethyl-l,3- propanediol diacetate, and the like.

The hydroxyalkyl substituted amides and their esters described may be prepared for example by the following procedure: The calculated amount of fatty acid anhydride, for amide or ester forma tion as desired is added to an equivalent quantity of a primary amino hydroxy compound based on its neutralization equivalent and the resultant mixture heated, for example on a steam bath, for a period of about two hours. At the end of this time the low boilers may be stripped off with a vacuum pump, and the residue recovered as the N-substituted amide, the yields varying from approximately to The crude prodnot thus prepared is usually sufficiently pure for satisfactory use as a plasticizer in the various synthetic elastomers, but if desired it may be further purified by vacuum distillation or otherwise. The compounds covered by this generic formula also can be prepared, in general, by other methods well known to the art. For instance, they may be prepared by the action of a fatty acid chloride, in a suitable medium, on the aminohydroxy compound. The N-(hydroxyalkyl) amides often can be prepared by reaction, in the known manner, of a fatty acid ester on the aminohydroxy compound, or by a direct .controlled reaction of the fatty acid itself on the aminohydroxy compound.

The amount of plasticizer utilized will vary with the relative difficulty of plasticization of the particular elastomer involved and with the degree of softness desired. In general, such sofare tested for these factors in the tenets can be employed in a.

tensile teste As illustrative of my gation.

tional manner.

Test composition Parts by Weight Hycar OR (butadiene-acrylonitrlle copolymer) 100 Zinc oxide Stearic acid 1 Altax (benzothiazyl disulfide) 1.5 Sulfur 1.5 Carbon 50 Plasticizer 189.0 After milling, part of each sample was subjected to tensile and elongation tests, part was tested in the extrusion plastometer with the results given below Table Extrusion Time in Seconds at- Plasticizcr Tensile Elong.

5% lbs. 7%lbs. Unplasticized batch 2, 280 247 738 210 2-Acetamidobutyl acetate" 560 357 34 18 2-Acemmido-2-methyl-1,3-

propanedinl diacctate 1i. 3, 400 410 8 3 2-Hexan nmido-l-butanoL 2, 240 365 12 3 2Acctamido-l-butanol. 2, 270 350 25 8 Dibutyl phthalatc (control) 2, 980 480 37 19 Tricrosyl phosphate (0011' In the above table, a reduction in extrusion time indicates an increase in plasticity, that is with such tests for comparison.

It will also be observed, that in general, the

What is claimed is: 1. A composition comprising a synthetic rubber-like elastomer of the with structure H2C=C and 2acetamido-2-methyl-1,3-propanedi0l diacetate the latter being present in plasticizlng proportions.

2. A composition comprising a her-like 1,3-butadiene acrylonitrile copolymer diene polymerized the polymerizable o H R1 H lium-R:

alkyl radical having represents a suba substituent selected from the group consisting of ethyl and 3. The composition of claim 2 wherein the N- substituted amide is 2-acetamido-1-butanol.

4. The composition of claim 2 wherein the N- substituted amide is 2-hexanamido-1-butanol.

PHILIP F. TRYON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PA ENTS Number Name Date 2,250,664 Watkins July 29, 1941 2,284,609 Schroy May 26, 1942 2,325,947 Garvey Aug. 3, 1943 OTHER REFERENCES Karrer, Organic Chemistry, Elsevier," Nordeman Publishing Company, Inc., New York, New York (1938 page 181. (Copy in Division 50.)

Ind. & Eng. Chem, article by Fisher, pages 941-945, vol. 31, No. 8, August 1939. Division 50.) 

